JP2012526900A - Phosphorus-containing flame retardant - Google Patents

Abstract

（式中、AはO、S、SO₂、単結合、アルキル、及び-CH₂-P¹から選択され、P¹は式:

の燐含有基であり、R¹及びR²は同じか異なり、各々はH、O-アルキル、O-アリール、アルキル、アリール、及びOMから選択され、R³はH又はアルキルであり、M=Na,K,Zn,Al,Ca、aは、各ポリマー鎖に対して少なくとも１単位であるという条件で、０〜４の整数であり、nは１〜１００，０００の整数であり、mは０〜１００，０００の整数である。）
の少なくとも一つを有する有機燐化合物（B）を含む。The flame retardant resin composition comprises a base resin (A) such as polyester, polyamide or polycarbonate resin, and the following formulas (I), (II) and (III):

Wherein A is selected from O, S, SO ₂ , a single bond, alkyl, and —CH ₂ —P ¹ , where P ¹ is the formula:

Wherein R ¹ and R ² are the same or different, each selected from H, O-alkyl, O-aryl, alkyl, aryl, and OM, R ³ is H or alkyl, and M = Na, K, Zn, Al, Ca, a is an integer of 0-4, n is an integer of 1-100,000, provided that it is at least 1 unit for each polymer chain, m is It is an integer from 0 to 100,000. )
An organic phosphorus compound (B) having at least one of the following.

Description

  The present invention relates to, but is not limited to, a phosphorus containing flame retardant, particularly for glass filled polyamide resins.

  The use of engineering plastics for electronic applications has grown substantially with current and future market demands for electrical components towards lighter plastic parts with improved electrical and mechanical properties. . Currently, polyamides are the primary engineering thermoplastics for electronic applications and the like, especially when reinforced with glass fillers to increase their structural and impact strength and stiffness.

  Polyamides are generally characterized by being relatively thermally stable after prolonged exposure to processing temperatures and shear forces. However, when exposed to flame, they burn quite easily, and the flammability is characterized by the dripping behavior of the burning resin. Accordingly, there is a substantial demand for flame retardant polyamides, particularly flame retardant glass filled polyamides. Similarly, there is a need for these polyester resins, typically glass reinforced, and the choice of resin depends on several factors such as a balance between cost and mechanical performance.

  One of the main types of flame retardants for thermoplastics and polyurethane foams is the organophosphorus compounds (typically phosphates and phosphonates). These may be non-halogenated or may contain a mixture of a phosphorus / halogen compound and a phosphorus compound and a halogenated flame retardant, typically a brominated flame retardant.

  In general, organophosphorus compounds provide flame retardant activity through a combination of condensed phase reaction, polymer carbonization promotion, and carbide formation. These processes obviously depend on the polymer in which such additives are present. Thus, specific phosphorus-containing structures need to be designed for various polymer types.

  For example, U.S. Pat. No. 3,681,281 discloses a polyester, at least 1 weight percent tertiary phosphine oxide of the polyester, and about 10 to about 50 weight percent of triphenylmelamine, benzyl, of the tertiary phosphine oxide. , As well as a molded structure comprising a synergist selected from the group consisting of dibenzyl. Among the tertiary phosphine oxides, xylylene bis-diphenylphosphine oxide is exemplified.

Industrial & Engineering Chemistry Product Research and Development, (1982), 21 (2), pages 328-31 “Phosphorus-based additives for flame retardant polyesters. In a paper titled 'Low Molecular Weight Additives', Robert W Stackman has shown that various phosphorus-containing organic compounds, including xylene bis-diphenylphosphine oxide, are difficult for poly (ethylene terephthalate) and poly (1,4-butylene terephthalate). It is evaluated as a flame retardant. The evaluation is based on the effect of the additive on the melt stability of the preformed polymer and on the flammability of the film as measured by the non-standard bottom burn oxygen (oxygen index method). Includes effects. The oxygen index value for these mixtures was a function of the phosphorus content of the mixture. The efficiency of the phosphorus compound as a flame retardant changed in the order of R ₃ PO> R (R′O) ₂ PO> (R′O) ₃ PO according to the change in the type of the phosphorus structure. Polymer additives have been reported to be attractive additives that give a combination of high flame retardance and low performance degradation due to mixing, even at 20 wt% or less of the mixture.

  Other organophosphorus compounds have also been suggested for use as flame retardants for polyamides. For example, Research Disclosure 168051 (published April 1978) entitled “Improved Nylon” describes flakes of bis (4-aminocyclohexyl) methane-dodecanedioic acid copolymer. Using a screw melter coated with 8-10% p-xylylene bis (diphenylphosphine oxide) flame retardant and equipped with a homogenized in-line mixer, the molten polymer was fed into a 34-filament yarn production device and the yarn was A flame retardant nylon fiber produced by spinning is described. The molten polymer was heated to 300-10 ° and the residence time was about 15 minutes. The yarn was drawn 2.3 times on a hot tube to produce a 100 denier yarn.

（式中、R₁及びR₃は水素、フェニル及び１〜４個の炭素原子のアルキル基から成る群から選択される任意の基であり、R₂は水素、フェニル及び２〜４個の炭素原子のアルキル基から成る群から選択される任意の基であるが、但し、R₁及びR₃が水素基である場合、R₂は２〜４個の炭素原子のアルキル基又はフェニル基である。）
を有する有効量のトリス-(3-ヒドロキシアルキル)ホスフィンオキシドを組み合わせることにより難燃性にした、ガラス充填熱可塑性ポリアミドポリマーを開示している。 Further, U.S. Pat. No. 4,341,696 has the formula:

Wherein R ₁ and R ₃ are any groups selected from the group consisting of hydrogen, phenyl and alkyl groups of 1 to 4 carbon atoms, and R ₂ is hydrogen, phenyl and 2 to 4 carbons. An arbitrary group selected from the group consisting of an alkyl group of atoms, provided that when R ₁ and R ₃ are hydrogen groups, R ₂ is an alkyl group of ₂ to 4 carbon atoms or a phenyl group .)
Disclosed is a glass-filled thermoplastic polyamide polymer rendered flame retardant by combining an effective amount of tris- (3-hydroxyalkyl) phosphine oxide having:

のホスフィネート塩、及び（又は）、式：

のジホスフィネート塩、及び（又は）、それらのポリマー（式中、R¹,R²は同じ又は異なり、各々線状又は分岐状のC₁-C₆-アルキル及び(又は)アリールであり、R³は線状又は分岐状のC₁-C₁₀-アルキレン、C₆-C₁₀-アリーレン、-アルキルアリーレン又は-アリールアルキレンであり、MはMg、Ca、Al、Sb、Sn、Ge、Ti、Zn、Fe、Zr、Ce、Bi、Sr、Mn、Li、Na及び（又は）Kであり、mは１〜４であり、nは１〜４であり、xは１〜４である。）を、成分Bとして、０〜５０重量％の、窒素含有相乗剤又は燐/窒素難燃剤を、そして、成分Cとして、０．１〜１０重量％の液体成分を含有する、ポリエステル及びポリアミドを含む熱可塑性及び熱硬化性ポリマー用の、難燃性配合物を開示している。 US Pat. No. 7,332,534, as flame retardant component A, is 90 to 99.9% by weight of the formula:

The phosphinate salt of and / or the formula:

And / or their polymers (wherein R ¹ and R ² are the same or different and are each linear or branched C ₁ -C ₆ -alkyl and / or aryl, R ³ Is linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, -alkylarylene or -arylalkylene, M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and / or K, m is 1 to 4, n is 1 to 4, and x is 1 to 4. Heat comprising polyester and polyamide, containing 0 to 50% by weight of nitrogen-containing synergist or phosphorus / nitrogen flame retardant as component B and 0.1 to 10% by weight of liquid component as component C Flame retardant formulations are disclosed for plastic and thermoset polymers.

（式中、Arは芳香族炭化水素環、又は窒素含有芳香族複素環を表し、X¹は酸素原子又は硫黄原子を表し、Y¹及びY²は同じ又は異なり、各々は炭化水素基、アルコキシ基、アリールオキシ基、又はアラルキルオキシ基を表し、Z¹はアルキレン基、又はアルキルアミンに対応する窒素含有二価基を表し、Y¹及びY²は互いに結合しても良く、又Y¹及びY²は隣接する燐原子と一緒に環を形成しても良く、『a』は０又は１を示し、『b』は１〜６の整数を示す。）
により表される単位を有する有機燐化合物（B）、及び難燃性助剤（C）を含む難燃性樹脂組成物を開示している。 US Pat. No. 7,411,013 describes a base resin (A) such as polyester, polyamide, or styrenic resin, having the following formula:

(In the formula, Ar represents an aromatic hydrocarbon ring or a nitrogen-containing aromatic heterocyclic ring, X ¹ represents an oxygen atom or a sulfur atom, Y ¹ and Y ² are the same or different, and each represents a hydrocarbon group, alkoxy A group, an aryloxy group, or an aralkyloxy group, Z ¹ represents an alkylene group or a nitrogen-containing divalent group corresponding to an alkylamine, Y ¹ and Y ² may be bonded to each other, and Y ¹ and Y ² may form a ring together with the adjacent phosphorus atom, “a” represents 0 or 1, and “b” represents an integer of 1 to 6.)
The flame retardant resin composition containing the organophosphorus compound (B) which has a unit represented by this, and a flame retardant adjuvant (C) is disclosed.

  According to the present invention, certain benzyl-substituted phosphorous oxide compounds are highly effective flame retardants for thermoplastics including polyamides, particularly glass-filled polyamides, especially when combined with certain synergists, It has now been discovered.

US Pat. No. 3,681,281 U.S. Pat. No. 4,341,696 US Pat. No. 7,332,534 US Pat. No. 7,411,013

Industrial & Engineering Chemistry Product Research and Development, (1982), 21 (2), pages 328-31 “Phosphorus-based additives for flame retardant polyesters. Paper titled “Low Molecular Weight Additives” Research Disclosure 168051 entitled “Improved Nylon” (published April 1978)

（式中、AはO、S、SO₂、単結合、アルキル、及び-CH₂-P¹から選択され、
P¹は式:

の燐含有基であり、
R¹及びR²は同じか異なり、各々はH、O-アルキル、O-アリール、アルキル、アリール、及びOMから選択され、
R³はH又はアルキルであり、
M=Na,K,Zn,Al,Caであり、
aは、各ポリマー鎖に対して少なくとも１単位であるという条件で、０〜４の整数であり、
nは１〜１００，０００の整数であり、mは０〜１００，０００の整数である。）
の少なくとも一つにより表される単位を含む有機燐化合物（B）、並びに、所望により少なくとも１種の難燃性補助物質（C）を含む、難燃性樹脂組成物に在る。 Accordingly, the present invention in one aspect provides the base resin (A), the following formulas (I), (II) and (III):

Wherein A is selected from O, S, SO ₂ , a single bond, alkyl, and —CH ₂ —P ¹ ;
P ¹ is the formula:

A phosphorus-containing group of
R ¹ and R ² are the same or different and each is selected from H, O-alkyl, O-aryl, alkyl, aryl, and OM;
R ³ is H or alkyl;
M = Na, K, Zn, Al, Ca,
a is an integer from 0 to 4, provided that it is at least 1 unit for each polymer chain;
n is an integer of 1 to 100,000, and m is an integer of 0 to 100,000. )
The flame retardant resin composition contains an organophosphorus compound (B) containing at least one unit represented by: and optionally at least one flame retardant auxiliary substance (C).

  Conveniently, the organophosphorus compound (B) is present in an amount of about 10 to about 30% by weight of the flame retardant resin composition.

  Conveniently, at least one flame retardant auxiliary substance (C) is present and is selected from melamine salts, inorganic metal compounds, clay materials, double layered hydroxide materials, and polyphenylene ether resins. .

  The at least one flame retardant auxiliary material (C) advantageously comprises a melamine salt and an inorganic metal compound in a weight ratio between about 10: 1 and about 1: 1.

  The inorganic metal compound advantageously comprises a metal salt such as a borate, in particular zinc borate.

  The melamine salt advantageously comprises melamine phosphate, in particular melamine polyphosphate or melamine pyrophosphate.

  Conveniently, the at least one flame retardant auxiliary substance (C) is present in an amount of from about 1 to about 20% by weight of the flame retardant resin composition.

  Conveniently, the base resin (A) contains at least one of a thermoplastic or thermosetting resin. A typical thermosetting resin is an epoxy resin, and a typical thermoplastic resin is a polyester, polyamide, polycarbonate, or styrenic resin.

  In one embodiment, the base resin (A) comprises a polyamide, particularly a glass-filled polyamide, typically one containing glass at about 15 and about 40% by weight of the total weight of the polyamide and glass.

Here, a flame retardant resin composition containing a base resin (A), a benzyl-based substituted organophosphorus compound (B), and optionally at least one flame retardant auxiliary substance (C) is described.
Base resin

  The base resin may be any organic polymer such as polyester resin, styrene resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, vinyl resin, olefin resin, acrylic resin, or epoxy resin. It may be. The base resin may be a thermoplastic or thermosetting resin. Particularly preferred are engineering resins such as polyester resins, polyamide resins and polycarbonates, especially glass filled polyesters and polyamides.

  The polyester resin includes, for example, a homopolyester and a copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component and polycondensation of a hydroxycarboxylic acid or a lactone component. Preferred polyester resins usually include saturated polyester resins, particularly aromatic saturated polyester resins such as polybutylene terephthalate.

  Polyamide resins are polyamides derived from diamines and dicarboxylic acids, if necessary in combination with diamines and / or dicarboxylic acids, polyamides obtained from aminocarboxylic acids, and if necessary with diamines and / or dicarboxylic acids. In combination, includes a polyamide derived from lactam. The polyamide also includes copolyamides derived from at least two different polyamide components.

  Suitable polyamide-based resins include aliphatic polyamides (eg, nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, and nylon 12), aromatic dicarboxylic acids (eg, terephthalic acid, and / or) Isophthalic acid) and aliphatic diamines (eg hexamethylene diamine, nonamethylene diamine) and polyamides obtained from both aromatic and aliphatic dicarboxylic acids (eg both terephthalic acid and adipic acid) and aliphatic diamines ( For example, polyamides obtained from hexamethylenediamine are included. These polyamides may be used alone or in combination.

  The base resin may be mixed with a filler to modify its properties such as mechanical strength, stiffness, thermal stability, and electrical conductivity. The filler may be fibrous or non-fibrous. Suitable fibrous fillers include glass fibers, asbestos fibers, carbon fibers, silica fibers, fibrous wollastonite, silica-alumina fibers, zirconia fibers, potassium titanate fibers, metal fibers, and organic fibers having a high melting point ( For example, aliphatic or aromatic polyamide, aromatic polyester, fluorine-containing resin, acrylic resin such as polyacrylonitrile). Suitable non-fibrous fillers include plate-like (or layered) fillers such as kaolin, talc, glass flake, mica, graphite, metal foil, and layered phosphates (eg, zirconium phosphate and titanium phosphate). . Further, carbon black, white carbon, silicon carbide, silica, silica powder, glass beads, glass powder, milled fibers (eg milled glass fiber), silicates (eg calcium silicate, aluminum silicate) , Clay, diatomaceous earth), metal oxides (eg, iron oxide, titanium oxide, zinc oxide, and alumina), metal carbonates (eg, calcium carbonate, and magnesium carbonate), metal sulfates (eg, calcium sulfate, and sulfuric acid) Barium), as well as metal powders, particulate or amorphous fillers can also be used.

Preferred fillers include glass fibers and carbon fibers. In one embodiment, the base resin comprises a glass filled polyamide containing glass fibers at about 15 and about 40% by weight of the total weight of the polyamide and glass.
Organophosphorus compounds

（式中、Aは、O、S、SO₂、単結合、アルキル、及び-CH₂-P¹から選択され、
P¹は式:

の燐含有基であり、
R¹及びR²は同じか異なり、各々はH、O-アルキル、O-アリール、アルキル、アリール、及びOMから選択され、
R³はH又はアルキルであり、
M=Na,K,Zn,Al,Caであり、
aは、各ポリマー鎖に対して少なくとも１単位であるという条件で、０〜４の整数であり、
nは１〜１００，０００の整数であり、mは０〜１００，０００の整数である。）
の少なくとも一つにより表すことが出来る。 The organophosphorus compound used in the flame retardant resin composition has the following formulas (I), (II) and (III):

Wherein A is selected from O, S, SO ₂ , a single bond, alkyl, and —CH ₂ —P ¹ ;
P ¹ is the formula:

A phosphorus-containing group of
R ¹ and R ² are the same or different and each is selected from H, O-alkyl, O-aryl, alkyl, aryl, and OM;
R ³ is H or alkyl;
M = Na, K, Zn, Al, Ca,
a is an integer from 0 to 4, provided that it is at least 1 unit for each polymer chain;
n is an integer of 1 to 100,000, and m is an integer of 0 to 100,000. )
Can be represented by at least one of the following.

が含まれる。 Representative benzylic substituted organophosphorus compounds of the above formula include diphenyl phosphine oxide derivatives of diphenyl ether (lower compound V), diphenyl phosphine oxide derivatives of diphenoxybenzene (lower compound VI), diphenyl phosphine oxides of aryl ether oligomers. Derivatives (lower compound VII), diphenylphosphine oxide derivatives of polyphenylene ether (lower compound VIII), diphenylphosphine oxide derivatives of polystyrene (lower compound IX), and p-xylylenebis (diphenylphosphine oxide) (lower compound X ):

Is included.

Conveniently, the organophosphorus compound (B) is present in an amount of about 10 to about 30% by weight of the flame retardant resin composition.
Flame retardant auxiliary substances

  In order to promote the flame retardancy, the resin composition can contain at least one flame retardant auxiliary substance in addition to the above-described organic phosphorus compound. Suitable flame retardant auxiliary materials include melamine salts, inorganic metal compounds, clay compounds, double layered hydroxide materials, polyphenylene ether resins, and mixtures thereof.

  Suitable melamine salts include salts of melamine itself, as well as substituted melamines (eg, alkyl melamines such as 2-methylmelamine, guanylmelamine), melamine condensation products (eg, melam, melem, melon), and Salts of melamine derivatives such as melamine copolycondensation resins (eg, melamine / formaldehyde resin, phenol / melamine resin, benzoguanamine / melamine resin, and aromatic polyamine / melamine resin) are included. Generally, the salts include the melamine, nitric acid, chloric acid (eg, perchloric acid, chloric acid, chlorous acid, hypochlorous acid), phosphorous acid, sulfuric acid, sulfonic acid, boric acid, chromic acid, antimonic acid, Produced by reaction with an oxygen-containing acid such as molybdic acid, tungstic acid, stannic acid, or silicic acid.

  Examples of suitable melamine salts include melamine orthophosphate, melamine phosphate, melamine pyrophosphates (including melamine pyrophosphate, and dimelamine pyrophosphate), melamine polyphosphate (melamine triphosphate) Including phosphate and melamine / tetraphosphate), melamine sulfates (including melamine sulfate, dimelamine sulfate, and guanylmelamine sulfate), melamine / pyrosulfates (eg, melamine / pyrosulfate, and dimelamine) Pyrosulfate), melamine sulfonates (eg, melamine methane sulfonate, melam methane sulfonate, and melem methane sulfonate), and melamine orthoborate (eg, mono-trimelamine orthoborate) ) Is included.

  Preferred melamine salts are melamine pyrophosphates.

  Suitable inorganic metal compounds for use in the synergist combination of the present invention include metal salts of inorganic acids, metal oxides and hydroxides, and metal sulfides.

  When the inorganic metal compound is a metal salt of an inorganic acid, suitable inorganic acids include phosphorous acids (eg, orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphoric acid, pyrophosphoric acid, polyphosphoric acid, anhydrous Phosphoric acid and polymetaphosphoric acid), boric acid (eg, orthoboric acid, metaboric acid, pyroboric acid, tetraboric acid, pentaboric acid, and octaboric acid), stannic acid (eg, stannic acid, metastannic acid, orthostannic acid, and hexahydroxo) Stannic acid), molybdic acid, and tungstic acid.

  Examples of suitable metal salts include calcium pyrophosphate, calcium polymetaphosphate, alkaline earth metal hydrogen phosphates (eg, magnesium orthophosphate and calcium orthohydrogenphosphate), transition metal hydrogen phosphates (eg, phosphate) Manganese hydrogen, iron hydrogen phosphate, zinc hydrogen phosphate, and cadmium hydrogen phosphate), metal hydrogen phosphate of group 13 periodic table metal (for example, aluminum hydrogen phosphate), metal hydrogen phosphate of group 14 periodic table of elements (for example, Tin hydrogen phosphate), alkaline earth metal borates (eg, calcium orthoborate, calcium metaborate, calcium pyroborate, and trimagnesium tetraborate), transition metal borates (eg, manganese orthoborate, manganese tetraborate, diborate) Nickel, copper metaborate, zinc metaborate, zinc tetraborate, cadmium metaborate, and Cadmium raborate), alkali metal stannates (eg sodium stannate and potassium stannate), alkaline earth metal stannates (eg magnesium stannate), transition metal stannates (eg cobalt stannate) And zinc stannate), zinc molybdate, and zinc tungstate.

  Examples of suitable metal oxides and hydroxides include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide, nickel oxide, iron oxide, manganese oxide, trioxide Antimony, antimony tetroxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, tin hydroxide, and zirconium hydroxide are included. Mixed oxides such as aluminosilicate, including clay, can also be used.

  Examples of suitable metal sulfides include molybdenum sulfide, tungsten sulfide, and zinc sulfide.

  Preferred inorganic metal compounds are borates, especially zinc borate.

  In one embodiment, the flame retardant auxiliary material is a combination of melamine salt and inorganic metal compound in a weight ratio between about 10: 1 and about 1: 1.

  In another embodiment, the flame retardant auxiliary material is a carbide-forming organic compound such as a polyphenylene ether (PPE) type resin. A specific PPE resin example would be PPO 803 from Sabic Innovative Plastics. The PPE resin can be used in a loading typically between about 1% and about 25%, more typically between about 5% and about 15%.

The invention will be described more specifically with reference to the following examples.
[Example 1]: Production of diphenylphosphine oxide derivative (compound V) of diphenyl ether

Diphenyl ether (100 g), 50 g paraformaldehyde, and 400 mL acetic acid were stirred at 60 ° C. HCl (304 g) was bubbled through the solution for over 5 hours. After aqueous treatment with methylene chloride and concentration of the organic material, 146.1 g of clear liquid was obtained. ^{The 1} H NMR spectrum was consistent with the structure shown, indicating that the material was predominantly the para isomer. The clear liquid (120 g), 356 g ethyl diphenylphosphinite, and 500 g dichlorobenzene were stirred at 165 ° C. overnight. The product was isolated by crystallization and repeated digestion / washing to give compound V (137.0 g) as a white solid. Analysis: thermogravimetric analysis 5% weight loss: 342 ° C .; 10.3% P; differential scanning calorimetry (melting): 274.4, 279.2 ° C.
[Example 2]: Production of diphenylphosphine oxide derivative (compound VI) of diphenoxybenzene

Diphenoxybenzene (100 g), paraformaldehyde (45.6 g), 33% HBr in acetic acid (748 g), and methylene bromide (632 g) were stirred at 60 ° C. for several hours and then at 90 ° C. overnight. . After aqueous treatment and concentration, 214.7 g of a dark blue liquid was obtained. This dark blue liquid (210 g), ethyl diphenylphosphinite (439 g), and 1,2-dichlorobenzene (2 L) were heated at 160 ° C. overnight. The volatiles were removed using a Dean Stark trap. After cooling to room temperature, the reaction mass was filtered. The resulting white powder was slurried in hexane at room temperature and dried to give 162 g of material. This white powder product (135 g) was washed with acetone, and after filtration and drying, 95.0 g of compound VI was obtained as a solid. Analysis: Thermogravimetric analysis 5% loss: 290.9 ° C .; 9.85% P.
[Example 3]: Production of diphenylphosphine oxide derivative (compound VII) of an aryl ether oligomer

Compound 1C was prepared using a modification of the procedure described in German Patent Publication DE 3,334,068A1. Poly (phenylene ether) oligomer (90.0 g; n = 0-2), 54.95 g paraformaldehyde, 901 g 33% HBr in acetic acid, and 900 g dibromomethane heated at 60 ° C. with stirring for 4.5 hours. did. The reaction mixture was then brought to 90 ° C. and kept at that temperature overnight. The reaction mixture was then washed and the organic material was concentrated in vacuo to give 194.1 g of a brown solid intermediate. Analysis: organic bromide: 46.78%; ¹ H NMR (CDCl ₃ ): δ 7.54-6.64 (m); 4.64-4.41 (m).

This brown solid intermediate (186.9 g), 304 g of ethyl diphenylphosphinite, and 3 L of 1,2-dichlorobenzene were heated at 160 ° C. overnight with stirring under one side of nitrogen. The volatiles were removed using a Dean Stark trap. The reaction mass was concentrated under vacuum. The concentrate (256.6 g) was heated with stirring at 175 ° C. overnight with 256 g of 1,2-dichlorobenzene and 56 g of ethyl diphenylphosphinite. The reaction mixture was then cooled to room temperature and reprecipitated with hexane. After filtration and vacuum drying, 251 g of compound VII was obtained as a white solid. Analysis: thermogravimetric analysis 5% loss: 314.2 ° C .; 10.26% P; ³¹ P NMR (CDCl ₃ ): δ-21.70 (m).
[Example 4]: Production of diphenylphosphine oxide derivative (compound VIII) of substituted polyphenylene ether

Polyphenylene ether resin (PPO 803 resin from GE Plastics) (45 g), 22.5 g paraformaldehyde, 367.4 g 33% HBr in AcOH, and 150 g methylene bromide were stirred and heated at 60 ° C. overnight. did. After treatment, the organic material was precipitated in acetone. Upon drying, 78.9 g of white powder was obtained. Analysis: ¹ H NMR (CDCl ₃ ): δ 6.07 (m), 4.75 (m), 4.2-1.90 (m). The white powder (70.0 g), 151.3 g ethyl diphenylphosphinite, and 1,2-dichlorobenzene (2 L) were heated at 160 ° C. overnight. The volatiles were removed using a Dean Stark trap. The reaction mixture was then concentrated to half volume by distillation. The concentrated reaction mixture was precipitated with acetone and then reprecipitated. After filtration and drying, 93.1 g of compound VIII was obtained as a white powder. Analysis: Thermogravimetric analysis 5% loss: 353.1 ° C .; 8.73% P.
[Example 5]: Production of diphenylphosphine oxide derivative (compound IX) of polystyrene

Poly (vinylbenzyl chloride) (77.5 g), 349 g of ethyl diphenylphosphinite, and 430 g of 1,2-dichlorobenzene were heated at 160 ° C. overnight with stirring under a blanket of nitrogen. The volatiles were removed using a Dean Stark trap. The reaction mixture was taken up in 300 mL of methylene chloride and the product was precipitated with hexane and then reprecipitated. After washing, filtration and drying, compound IX was obtained as 138 g of tan powder. Analysis: differential scanning calorimetry (Tg): 125.7 ° C .; thermogravimetric analysis 5% loss: 350.2 ° C .; 9.58% P.
[Example 6]: Production of p-xylenebis (diphenylphosphine oxide) (compound X)

  Inst. Elementoorg. Soedin. Moscow, USSR. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya 1979, (11), 2572-5, using the procedure described by Bodrin, G.V. Ethyl diphenylphosphinite (522 g), 180 g α, α′-dichloro-p-xylene, and 2,400 g 1,2-dichlorobenzene are stirred while heating at 160 ° C. overnight under a nitrogen surface. did. The volatiles were removed using a Dean Stark trap. The mixture was then cooled to room temperature and filtered. The resulting wet cake was washed with hexane. After filtration and subsequent vacuum drying, Compound X was obtained as 487 g of a white powder. Analysis: Thermogravimetric analysis 5% loss: 365 ° C .; 12.0% P.

Example 7: Use of Flame Retardant in Glass Reinforced PA66 Various flame retardant compounds described in Examples 1-6 were used to produce PA66 resin and PA66 glass concentrate to produce the desired 30% glass fiber reinforcement. These were compounded by mixing the materials using a twin screw extruder using or in a vented Brabender processor. In the Brabender processor, the sample was mixed at 265 ° C. for 4 minutes. About 3 minutes after the start of mixing, glass fiber was added over about 15 seconds to produce the desired 30% glass fiber reinforcement. The compounded material was ground on a Thomas Wiley mill and then molded by using a small injection molding machine at 265 ° C. to form a 1/16 inch thick UL-94 specimen.

a) DuPontからの４３％ガラス・PA66樹脂濃縮物。
b) BD=燃焼滴下：該試験片からの燃焼物質が綿（コットン）に火をつけたことを示す。BTC=掴み具（クランプ）まで完全に燃焼した。
c) 1/32インチ厚試料片に関するUL試験。 The specimens were subjected to a UL-94 vertical burn test procedure in which the specimens were subjected to two 10 second flame applications. The time that the specimen extinguishes after each application is recorded and reported for the specimen as Time 1 (T1) and Time 2 (T2). The average burn time for 5 specimens was recorded for both flame applications (T1, T2). While observing any dripping behavior, the total burn time was summed over all five specimens for each of the two flame applications. The results are shown in Table 1.

a) 43% glass / PA66 resin concentrate from DuPont.
b) BD = burning dripping: Indicates that the burning material from the test piece ignited cotton. BTC = burned completely to the grip (clamp).
c) UL test on 1/32 inch thick specimen.

  As demonstrated in Table 1, the addition of 30% compound (compound) V, VI, or VIII showed flame retardancy to give a V-2 rating. Addition of 20 or 30% of Compound X material also gives a no-drop result with reduced burning time, or compared to the control standard (Formulation 1) by reducing burning time during the test. And showed flame retardancy. Formulation 6 was slightly less than reaching V-0 rating.

a) DuPontからの４３％ガラス・PA66樹脂濃縮物。
b) PPE=GE Plastics（現在のSabic Innovative Plastics）からのPPO 803/808。
c) MP-200=Melapur 200. Cibaからのメラミン・ポリ燐酸塩。
d) Budit 3141=Budenheimからのメラミン・ポリ燐酸塩；Budit 311= Budenheimからのメラミン・ピロ燐酸塩。
e) BD=燃焼滴下：該試験片からの燃焼物質が綿（コットン）に火をつけたことを示す。BTC=掴み具（クランプ）まで完全に燃焼した。 Example 8: Use of flame retardants and melamine or PPE-based auxiliary materials in glass reinforced PA66. Formulations were made as described in Example 7 and the molded specimens were burned as shown in Table 2 Tested for sex. Various melamine base materials as flame retardant auxiliary compounds were also added to the formulation and the effect on flammability was measured. In this system, PPE resin was also tested as a flame retardant auxiliary. The specimens were subjected to the UL-94 vertical burn test procedure and the average burn time for 5 specimens was recorded for both flame applications (T1, T2). While observing any dripping behavior, the total burn time was summed over all five specimens for each of the two flame applications.

a) 43% glass / PA66 resin concentrate from DuPont.
b) PPO 803/808 from PPE = GE Plastics (currently Sabic Innovative Plastics).
c) MP-200 = Melapur 200. Melamine polyphosphate from Ciba.
d) Budit 3141 = melamine polyphosphate from Budenheim; Budit 311 = melamine pyrophosphate from Budenheim.
e) BD = burning dripping: indicates that the burning material from the test piece ignited cotton. BTC = burned completely to the grip (clamp).

  These formulations show an increase in flame retardancy compared to Control Formula 1 (Table 1), and in most cases when used in combination with a melamine based flame retardant auxiliary substance V-0 flame retardant performance is shown. In addition, the use of organic-based carbide-forming flame retardant auxiliary materials such as PPE resins also improved the flame retardancy. When melamine compounds were used, the addition of zinc borate helped to remove dripping and gave a V-0 rating.

a) BD=燃焼滴下：該試験片からの燃焼物質が綿（コットン）に火をつけたことを示す。 Example 9: Use of flame retardant and glass / LDH based flame retardant auxiliary in glass reinforced PA66 Formulations were prepared as described in Example 7. Clay from Southern Clay Products, Cloisite 30B, was used as a flame retardant auxiliary material and its effect on flammability was measured. This clay is a quaternary ammonium salt modified natural montmorillonite material. In addition, a Zn ₂ Al (OH) ₆ zinc-aluminum double layered hydroxide (LDH) material was tested as an auxiliary material. The specimens were subjected to the UL-94 vertical burn test procedure and the average burn time for 5 specimens was recorded for both flame applications (T1, T2). While observing any dripping behavior, the total burn time was summed over all five specimens for each of the two flame applications. The results are summarized in Table 3.

a) BD = burning dripping: indicates that the burning material from the test piece ignited cotton.

  The data in Table 3 clearly shows the flame retardant effect of using these types of materials in resin formulations. Formulation 14 with only clay added as a control showed no dripping at all, but a very long burning time. The addition of various amounts of compound X improved the flame retardancy to V-1 and then to V-0 at higher loadings. The use of other benzylic polymer flame retardants, compounds VII and IX, also demonstrated the generality of this approach and good flame retardancy. When LDH was used instead of clay, some dripping behavior was shown and a V-2 rating was obtained.

Example 10: Use of Flame Retardant in Unreinforced PA66 Formulation To test the effect of glass fiber reinforcement and to determine whether these materials are flame retardant even in the absence of such reinforcement, see above. Formulations were prepared as described above and the molded specimens were tested for flammability as shown in Table 4. The specimens were subjected to the UL-94 vertical burn test procedure and the average burn time for 5 specimens was recorded for both flame applications (T1, T2). While observing any dripping behavior, the total burn time was summed over all five specimens for each of the two flame applications.

  The data in Table 4 also shows the usefulness of these materials as flame retardants in unreinforced resins. Addition of zinc borate as a flame retardant auxiliary further increased the flame retardant from V-1 to V-0.

  Although the invention has been described and described with reference to particular embodiments, those skilled in the art will appreciate that the invention is suitable for variations not necessarily described herein. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Claims (13)

Base resin (A) and the following formulas (I), (II) and (III):

Wherein A is selected from O, S, SO ₂ , a single bond, alkyl, and —CH ₂ —P ¹ ;
P ¹ is the formula:

A phosphorus-containing group of
R ¹ and R ² are the same or different and each is selected from H, O-alkyl, O-aryl, alkyl, aryl, and OM;
R ³ is H or alkyl;
M = Na, K, Zn, Al, Ca,
a is an integer from 0 to 4, provided that it is at least 1 unit for each polymer chain;
n is an integer of 1 to 100,000, and m is an integer of 0 to 100,000. )
A flame retardant resin composition comprising an organophosphorus compound (B) containing a unit represented by at least one of The organophosphorus compound (B) is a compound V to X:

The resin composition of Claim 1 containing one or more of these.   The resin composition according to claim 1 or 2, wherein the organic phosphorus compound (B) is present in an amount of 10 to 30% by weight of the flame retardant resin composition.   The resin composition according to any one of claims 1 to 3, comprising at least one flame retardant auxiliary substance.   5. The at least one flame retardant auxiliary material is selected from melamine salts, inorganic metal compounds, clay compounds, double layer hydroxide materials, and polyphenylene ether resins, and mixtures thereof. Resin composition.   The resin composition according to claim 5, wherein the inorganic metal compound is selected from metal salts of inorganic acids, metal oxides and hydroxides, metal sulfides, and mixtures thereof.   6. The resin composition according to claim 5, wherein the inorganic metal compound comprises a metal salt of an inorganic acid, preferably a borate, more preferably zinc borate.   6. Resin composition according to claim 5, wherein the melamine salt comprises melamine phosphate, preferably melamine polyphosphate and / or melamine pyrophosphate.   The resin composition according to any one of claims 4 to 8, wherein the at least one flame retardant auxiliary substance is present in an amount of 1 to 20% by weight of the flame retardant resin composition.   The resin composition according to any one of claims 1 to 9, wherein the base resin (A) contains at least one of polyester, polyamide, and polycarbonate resin.   The resin composition according to any one of claims 1 to 10, wherein the base resin (A) contains polyamide.   The resin composition according to any one of claims 1 to 11, wherein the base resin (A) comprises a glass-filled polyamide.   13. A polymer according to claim 12, comprising glass at 15 to 40% by weight of the total weight of the polyamide and glass.